Catalytic addition of stanne to olefins

ABSTRACT

This invention comprises a method for producing tetraorganotin compounds comprising reacting stannane, SnH4, and a compound selected from the group consisting of Alpha -olefinic compounds and cycloolefinic compounds in the presence of a catalyst and recovering said tetraorganotin compounds.

United States Patent Inventors Gerald ll. Rellenherg Hlghtstown; WilliamJ. Considine, Somerset, both of NJ. Appl. No. 742,165 Filed July 3, 1968Patented Sept. 21, 1971 Assignee M & T Chemicals Inc.

New York, N.Y.

CATALYTIC ADDITION OF STANNE T0 OLEFINS 14 Claims, No Drawings [56]References Cited FOREIGN PATENTS l,2l2,53l 2/l96l Germany 260/429.7OTHER REFERENCES Neumann et al. (ll), Angewandte Chemie, Vol. 2, No. 4,(1963), pages 165- l'75,QDlZ5 Primary ExaminerTobias E. Levow AssistantExaminer-Werten F. W. Bellamy Atlorneys- Kenneth G. Wheeless, Lewis C.Brown and Robert P. Grindle ABSTRACT: This invention comprises a methodfor produc- 7 CATALYTIC ADDITION OF STANNE T OLEFINS This inventionrelates to a novel process for the manufacture of organotin compounds.

This invention for the production of tetraorganotin compounds comprisesthe catalytic reaction of stannane, Snl-l and a compound selected fromthe group consisting of a-unsaturated olefinic compounds andcycloolefinic compounds in the presence of a catalyst and recoveringsaid tretraorganotin compounds.

According to another of its aspects, the method of this invention forproducing tetraorganotin compounds comprises reducing tin tetraorganotincompounds comprises reducing tin tetrahalide in the presence of lithiumaluminum hydride reducing agent or reducing stannous chloride in thepresence of sodium borohydride to produce stannane, Snl'l catalyticallyreacting said stannane, Snl l and a compound selected from the groupconsisting of a a-unsaturated olefinic compounds in the presence of acatalyst and recovering said tetraorganotin compounds.

Catalysts operable in the practice of this invention include: mixturesof cobalt soaps of organic acids exhibiting more than 6 carbon atomswith alkyl peroxides or hydroperoxides; hexachloroplatinic acid; andmixtures of palladium and charcoal.

According to one of its aspects, this invention for producingtetraorganotin compounds comprising reacting stannane,

SnH,,, and a compound selected from the group consisting of act-olefiniccompounds and cycloolefinic compounds in the presence of a catalyst andrecovering said tetraorganotin compounds.

Specific catalysts operable in reacting stannane, Snl-l witha-unsaturated olefinic compounds and cycloolefinic compounds includemixtures of cobalt naphthenate and di-t-butyl peroxide and mixtures ofcobalt naphthenate and tertiary butyl hydroperoxide. Other specificcatalysts include chloroplatinic acid and mixtures of palladium andcharcoal.

The addition reaction of stannane, Snl-l may be practiced witha-unsaturated olefins of the formula H C=CH-R' in which R may containvarious functional groups.

The reactant a-unsaturated olefins operable in the practice of thisinvention include ethylene, propylene, butenel, isobutene-l, pentene-l,hexene-l, heptene-l, and octene-l; substituted olefins such asacrylonitrile and cyclic olefins such as acrylonitrile and cyclicolefins such as cyclohexene.

In the compound R Sn, R is selected from the group consisting of,generally, lower substituted and unsubstituted alkyl and cycloalkylgroups.

When R is alkyl it may include ethyl, n-propyl, isobutyl, nbutyl, amyls,octyls, etc. When R is cycloalkyl it may include cyclohexyl,cycloheptyl, etc.

Stannane, Sui-l may be prepared by reacting tin tetrachloride, tintetrabromide or tin tetraiodide with lithium aluminum hydride in thepresence of a nitrogen atmosphere containing about 0.1 percent oxygen.Stannane, SnH.,, may also be produced by reducing stannous chloride inthe presence of sodium borohydride.

ln practicing the first step of this invention a tin tetrahalidecompound is reduced to stannane, Snl-l in the presence of lithiumaluminum hydride. The reduction may be preferably conducted, initially,at a temperature of -l95 C. maintained by immersion of the reactionvessel, or trap, in a liquid nitrogen bath. The reduction is preferablycarried out in a nitrogen atmosphere containing approximately 0.1percent,

by weight, oxygen. The reduction of tin tetrahalidemay be conducted inthe presence of an inert diluent or solvent, e.g. diethyl ether,tetrahydrofuran, tetrahydropyran, 2-methyl tetrahydrofuran and2-ethoxytetrahydropyran.

Tln carrying out the reduction of tin tetrahalide, said tin halideshould be contacted with lithium aluminum hydride at a temperatureranging from 200 C. to C. The temperature, initially, is preferably near200 C. and is preferably elevated slowly to 70 C. to avoid decomposingthat stannane which is the product of the reduction step. It is notedthat the melting point of stannane, Snl-h, is l46 C. and the boilingpoint is 52.5 C.

In reducing tin tetrahalide to stannane, SnH the molar ratio of reducingagent to tin tetrahalide should be greater than unity, preferably 2 or 3to 1.

During the reduction step, the following typical reaction may occur:SnCl +LiAlHF SnH +LiAlCl The practice of the second step of thisinvention may be effected by condensing an a-unsaturated olefin, or acycloolefinic compound into a reaction vessel or trap, containingsuitable catalysts; the vessel may be preferably immerse d in liquidnitrogen, the liquid nitrogen exhibiting a temperature of approximately1 C.

The reaction may proceed as follows: combination catalyst and initiator,e.g. cobalt naphthenate and ditertiary butyl peroxide are added to areaction vessel in a liquid nitrogen bath. The vessel is cooled toapproximately l95 C. by the liquid nitrogen bath. Stannane, Snl-l isthen added followed by the addition of an unsaturated organic compound.The reaction temperature may be adjusted to a higher temperature, circa.-78 C. by transferring the reaction temperature vessel or trap, from theliquid nitrogen bath (at l95 C.) to a dry ice acetone bath atapproximately 78 C.; and thereafter,

to an ice-methanol bath at -22" C. After removing the reaction mixturefrom the ice-methanol bath, the temperature is allowed to rise to roomtemperature. Unreacted stannane, Snl-l may be collected in conventionaltraps outside the reaction zone. The reaction mass may be filtered toseparate the product from the catalyst.

Solvents or diluents suitable as the reaction medium of this inventioninclude aliphatic hydrocarbons, aromatic hydrocarbons and ethers. Theforegoing may contain carboxylic esters, carboxylic amides, and nitrilegroups as substituents. Aromatic amino groups, but not aliphatic aminogroups, may also be present as substituents. Among the suitable solventsare diethyl ether and tetrahydrofuran.

Practice of this invention may be observed from the followingillustrative examples.

EXAMPLE 1 A 250 milliliter two-necked flask was placed in a liquidnitrogen bath at l96 C. The atmosphere surrounding the system wasnitrogen containing 0.1 percent oxygen, 6.5 grams (0.025 mole) of tintetrachloride and 4.8 grams (0.125 mole) of lithium aluminumhydride.'The temperature of the reaction vessel was slowly increased andat 62 C. ebullition of gas was observed. The temperature was slowly andincrementally increased to room temperature, 27 C., whereupon thestannane, SnH .product was collected in traps. The stannane productexhibited a weight of 2.65 grams, an 87.2percent yield. To a trap with aremovable head was added 60 milligrams of di-tertiary butyl peroxide andmilligrams of a hydrocarbon solution containing 6.0 percent cobaltnaphthenate (9 milligrams of cobalt naphthenate).

The reaction trap was then placed in a liquid nitrogen bath exhibiting atemperature (if- C. 2.65 grams (0.222 mole of stannane, SnH wereadded tothe reaction vessel, followed by the addition of 60 grams (0.1! mole) ofn-butene-l. The temperature of the reaction mass was then adjusted bysequentially transferring the reaction vessel from the liquid nitrogenbath to a dry ice-acetone bath exhibiting a temperature of approximately78 C. and then toan ice-methanol bath at 22C. The temperature of thereaction vessel was then allowed to risetoroom temperature. The producttetra-n-butyltin exhibited awveight of 2.24 grams (29.4 percent yield)and an index vof refraction 1.4696 the literature n l ,4727). Theidentification of the product was confirmed by infrared spectroscopicanalysis and vapor-phase chromatographic analysis.

EXAMPLE 2 The preparation of tetraethyltin The procedure of example 1was followed except that 4.8 grams (0.125 mole) of lithium aluminumhydride and 6.5 grams of tin tetrahalide were charged to the reactor forthe generation of 2.6 grams of stannane, Snl-1 For the reaction ofethylene with said 2.6 grams of stannane, Snl-l the reactor was chargedwith 3.0 grams (0." mole) of ethylene, 150 milligrams of a 6 percentsolution of cobalt naphthenate in hydrocarbon, and 90 milligrams oftertiary butyl hydroperoxide. The product, tetraethyltin, exhibited aweight of 1.65 grams, a yield of 33.5 percent; a refractive index of n=1.4666. The identification of the product was confirmed by vapor-phasechromatographic analysis.

EXAMPLE 3 The Preparation of tetracyclohexyltin The procedure of example1 was followed except that the reactor was charged with 2.7 grams (0.022mole) of stannane, SnH, and 8.0 grams of cyclohexene. The solid product,tetracyclohexyltin, exhibited a weight of 0.82 grams, a melting pointrange of 261 C. (the theoretical melting point being 262 C. 263C.) theidentification of the product was confirmed by infrared spectroscopicanalysis.

EXAMPLE 4 The Preparation of tetrapropyltin The procedure of example 1was followed except that the reactor was charged with 2.6 grams ofstannane, Snl-l and 4.0 grams of propylene. The product, tetrapropyltinexhibited a weight of 1.2 grams (a crude yield of 19.7 percent) and arefractive index of nD L4712. The identification of the product wasconfirmed by vapor-phase chromatographic analysis.

EXAMPLE 5 The Preparation of tetracyanoethyltin The procedure of example1 was followed except that the reactor was charged with 2.55 grams ofstannane, SnH 4.5 grams (0.084 mole) of acrylonitrile 300 milligrams ofcobalt naphthelate and 180 milligrams of tertiary butyl peroxide. Theproduct tetracyanoethyltin, a clear yellow oil, exhibited a weight of0.6 grams (a crude yield of 8.6 percent) and a refractive index ofn D=1.5312.

EXAMPLE 6 The preparation of tetraisobutyltin The procedure of example 1was followed except that the reactor was charged with 2.35 grams ofstannane, SHH4, 5.0 grams (0.09 mole) of isobutylene, 150 milligrams ofa 6 percent solution of cobalt naphthenate in hydrocarbon and 90milligrams of tertiary butyl hydroperoxide. The product tetraisobutylinexhibited a weight of 0.5 grams a yield of 14.4 percent. Theidentification of the product was confirmed by infrared spectroscopicanalysis EXAMPLE 7 The Preparation of tetrabutyltin The procedure ofexample 1 was followed except that the reactor was charged with 2.5grams of stannane, Snl-l 4.5 grams (0.08 mole) of butene-l and insteadof a catalyst mixture of di-tertiary butyl peroxide and cobaltnaphthenate, 0.25 grams of hexaclorplatinic acid was used. The producttetrabutyltin exhibited a weight of 1.6 grams, a crude yield of 23.2percent a refractive index of n =1.4705. The identification of theproduct was confirmed by vapor-phase chromatographic analysis.

EXAMPLE 8 The Preparation of Tetrabutyltin The procedure of example 1was followed except that the stannane, SnH generated exhibited a weightof 2.55 grams, an 83.1 percent yield, and that 60 milligrams of tertiarybutyl peroxide and 150 milligrams of 6 percent solution of cobaltnaphthelate in hydrocarbon were used instead of the catalyst mixture ofexample 1. The product, tetrabutyltin, exhibited a weight of 2.36 gramsand a refractive index of n l.4694. The identification of the productwas confirmed by infrared spectroscopic analysis and vapor-phasechromatographic analysis.

EXAMPLE 9 The Preparation of Tetrabutyltin Using Palladium As CatalystThe procedure of example 1 was followed except that the reaction of 2.4grams of stannane, Snl-l and 4.6 grams (0.08 moles 0 of butene-l wascatalyzed by 0.2 grams of charcoal impregnated with 10 percent, byweight, palladium. The product, tetrabutyltin, after filtrationexhibited a weight of 2.2 grams and a refractive index of n =l .4709.

EXAMPLE 10 The Preparation Of Tetrabutyltin Catalyzed By Tertiary ButylHydroperoxide The procedure of example 1 was used except that tertiarybutyl hydroperoxide was used instead of di-tertiary butyl hydroperoxidewas used instead of ditertiary butyl peroxide. The product,tetrabutylin, exhibited a weight of 3.46 grams, a yield of 47.4 percent,and a refractive index of nD =1.4697. The identification of the productwas confirmed by vaporphase chromatographic analysis.

EXAMPLE 1 l The Preparation Of tetraoctyltin The procedure of examplewas followed except that 2.65 grams (0.021 mole) of stannane, Snl-l and10.0 grams (0.084 mole of octene-l were charged to the reactor. Theproduct, tetroctyltin, exhibited a weight of 0.75 grams and an index ofrefraction of n D =l .4688.

Although this invention has been illustrated by reference to specificexamples, modifications thereof which are clearly within the scope ofthe invention will be apparent to those skilled in the art.

We claim:

1. A method for producing tetraorganotin compounds comprising placing acompound selected from the group consisting of a-unsaturated olefiniccompounds and cycloolefinic compounds. selected from the groupconsisting of ethylene, isobutylene, propylene, butene-l, isobutene-l,pentene-l, hexenel, octene-l, acrylonitrile, cyclohexene, andcycloheptene in a reaction zone with a catalyst selected from the groupconsisting of mixtures of cobalt soaps of an organic acid exhibiting 6carbon atoms and alkyl peroxides, mixtures of cobalt soaps of an organicacid exhibiting 6 carbon atoms and hydroperoxides, hexachloroplatinicacid, and mixtures of palladium and charcoal; adding stannane, Snl'h, tosaid reaction zone; reacting said stannane, Snl-l with said compound inthe presence of said catalyst for producing a tetraorganotin compound;and withdrawing said tetraorganotin compound from said reaction zone. I

2. A method as described in claim 1 in which the temperature of the saidreaction zone is maintained in the range of between about 1 C. and 22 C.

3. A method for producing tetraorganotin compounds comprising placingtin tetrahalide in a first reaction zone; adding lithium aluminumhydride to said first reaction zone; reducing said tin tetrahalide insaid first reaction zone while maintaining the temperature thereof inthe range of between about 200 C. and 70 C. to produce stannane, SnHplacing a compound selected from the group consisting of a-unsaturatedolefinic compounds and cycloolefinic compounds selected from the groupconsisting of ethylene, isobutylene, propylene, butene-l, isobutene-l,pentene-l, hexene-l, hepten-l, octene-l acrylonitrile, cyclohexene, andcycloheptene in a second reaction zone with a catalyst selected from thegroup consisting of mixtures of cobalt soaps of an organic acidexhibiting 6 carbon atoms and alkyl peroxides, mixtures of cobalt soapsof an organic acid exhibiting 6 carbon atoms and hydroperoxides,hexachloroplatinic acid, and mixtures of palladium and charcoal addingthe said stannane, Snl l produced in said first reaction zone to saidsecond reaction zone; reacting said stannane, Snl-l with said memberselected from the group consisting of a-unsaturated olefinic compoundsand cycloolefinic compounds in the presence of said catalyst forproducing a tetraorganotin compound; and withdrawing said tetraorganotincompound from said reaction zone.

4. A method as described in claim 3 in which the temperature of the saidsecond reaction zone is maintained in the range of between about -l 95C. and --22 C.

5. The method of claim 1 wherein said catalyst compriseshexachloroplatinic acid.

6. The method of claim 1 wherein said catalyst comprises mixtures ofpalladium and charcoal.

7 The method of claim 1 wherein said tetraorganotin compound istetraethyltin.

8. The method of claim 1 wherein said tetraorganotin compound istetreapropyltin.

9. The method of claim 1 wherein said tetraorganotin compound istetrabutyltin.

10. The method of claim 1 wherein said tetraorganotin compound istetracyanoethyltin.

11. The method of claim 1 wherein said tetraorganotin compound istetractyltin.

12. The method of claim 1 wherein said tetraorganotin compound istetracyclohexyltin.

13. The method of claim 3 wherein said catalyst compriseshexachlorplatinic acid.

14. The method of claim 3 wherein said catalyst comprises mixtures ofpalladium and charcoal.

Patent No.

Inventor(s) 3,607 ,892 Dated 9 21 71 Gerald H. Reifenberg 8: William J.Considine column 1,

Column 1,

Column Column Colunn Column 6,

(SEAL) Attest:

EDWARD M.FLETCHER,JR. Attesting Officer It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

line 1, for "stanne" read --stannane--.

line 28, for "aa-olefinic" read a-olefinic--.

line 12, following "charcoal" insert line 8, for "tetreapropyltin" read--tetrapropyltin--.

line 15, for "teractyltin" read --tetraoctylt:in--.

line 19, for "hexachlorplatinic" read --hexachloroplatinic-.

Signed and sealed this 11 th day of March 1972.

ROBERT GOTISCHALK Commissioner of Patents ORM PO-1050 {1069) USCOMM-DC603764 69 u s. eovennuzm PRINTING ornc: I955 O36633A

1. A method for producing tetraorganotin compounds comprising placing acompound selected from the group consisting of Alpha -unsaturatedolefinic compounds and cycloolefinic compounds selected from the groupconsisting of ethylene, isobutylene, propylene, butene-1, isobutene-1,pentene-1, hexene-1, octene-1, acrylonitrile, cyclohexene, andcycloheptene in a reaction zone with a catalyst selected from the groupconsisting of mixtures of cobalt soaps of an organic acid exhibiting 6carbon atoms and alkyl peroxides, mixtures of cobalt soaps of an organicacid exhibiting 6 carbon atoms and hydroperoxides, hexachloroplatinicacid, and mixtures of palladium and charcoal; adding stannane, SnH4, tosaid reaction zone; reacting said stannane, SnH4, with said compound inthe presence of said catalyst for producing a tetraorganotin compound;and withdrawing said tetraorganotin compound from said reaction zone. 2.A method as described in claim 1 in which the temperature of the saidreaction zone is maintained in the range of between about -195* C. and-22* C.
 3. A method for producing tetraorganotin compounds comprisingplacing tin tetrahalide in a first reaction zone; adding lithiumaluminum hydride to said first reaction zone; reducing said tintetrahalide in said first reaction zone while maintaining thetemperature thereof in the range of between about -200* C. and 70* C. toproduce stannane, SnH4; placing a compound selected from the groupconsisting of Alpha -unsaturated olefinic compounds and cycloolefiniccompounds selected from the group consisting of ethylene, isobutylene,propylene, butene-1, isobutene-1, pentene-1, hexene-1, hepten-1,octene-1, acrylonitrile, cyclohexene, and cycloheptene in a secondreaction zone with a catalyst selected from the group consisting ofmixtures of cobalt soaps of an organic acid exhibiting 6 carbon atomsand alkyl peroxides, mixtures of cobalt soaps of an organic acidexhibiting 6 carbon atoms and hydroperoxides, hexachloroplatinic acid,and mixtures of palladium and charcoal adding the said stannane, SnH4,produced in said first reaction zone to said second reaction zone;reacting said stannane, SnH4, with said member selected from the groupconsisting of Alpha -unsaturated olefinic compounds and cycloolefiniccompounds in the presence of said catalyst for producing atetraorganotin compound; and withdrawing said tetraorganotin compoundfrom said reaction zone.
 4. A method as described in claim 3 in whichthe temperature of the said second reaction zone is maintained in therange of between about -195* C. and -22* C.
 5. The method of claim 1wherein said catalyst comprises hexachloroplatinic acid.
 6. The methodof claim 1 wherein said catalyst comprises mixtures of palladium andcharcoal. 7 The method of claim 1 wherein said tetraorganotin compoundis tetraethyltin.
 8. The method of claim 1 wherein said tetraorganotincompound is tetreapropyltin.
 9. The method of claim 1 wherein saidtetraorganotin compound is tetrabutyltin.
 10. The method of claim 1wherein said tetraorganotin compound is tetracyanoethyltin.
 11. Themethod of claim 1 wherein said tetraorganotin compound is tetractyltin.12. The method of claim 1 wherein said tetraorganotin compound istetracyclohexyltin.
 13. The method of claim 3 wherein said catalystcomprises hexachlorplatinic acid.
 14. The method of claim 3 wherein saidcatalyst comprises mixtures of palladium and charcoal.